Manufacture of blue to greenish-blue coloring-matters of the gallocyanin series.



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urns rnrnnr onnion EMEL WfiLDER, 0F BASEL, SW ITZERLAND, ASSIGNOR T0CHEMICAL WORKS FORMERLY SlEiNDOZ, OF BASEL, S'WITEERLAND.

UFAGTUBE UP BLUE Ti GREENISH-BLUE CQLORINGJVZATTERQ OF THE GALLO-CE'ANIN SERIES.

lwgdli'yil. I ZIo Brewing; Application fllcdfiecem'oer 13, 1916.

To all whom it may concern:

3e it known that I, Dr. EMIL WALDEIR, a citizen of the Republic ofSwitzerland, re-

siding in Basel, Canton of Basel, Switzerland, have invented certain newand useful Improvements in the Manufacture of Blue It has been foundthat by the condensw tion of gollocyanins with mend p-aminobenzernid,end by reducing the insoluble condensation products so obtained, newcoloring ilnattei's are. obtained "which dye on chrome mordants blue andgreenish blue shades of considerable fastness to light, soap andchlorin, I v

The new condensationproducts end their respective leuco productscorrespond tothe following structuralformulm, in which stands or methyl(CH or ethyl (6 1-1 (Structuralformule or the condensation product of egallocyanm dye with III-211E11 (Structural formula of the leuco compoundof the condensation product or a gel locyemn dye with m-snnnobenzamid).

(Structural formula of the condensation {Specification oi LettersPatent.

Patented Apr. 1, 1919. Serial in). 186,742.

product of e gellocyenin dye with p-eminobenzmnid).

on mN -o- \-OH V'r r ONE \/'-coNH, (Structural formula of the leucocompound of the condensation product of e gaL locyenin dyewithp-aminobenzamid.) 4

The specifications of German Patents 166,679, 178,841 and 182,783describe condensstion products from gellocyenins with ommobenzoic acidswhich in the form. of

, their soluble alkali salts can be used directly for dyeing andprinting. These colors have, however, the disadvantage of being fixedonly after prolonged steaming. The leuco compounds whichcen be made fromthem in the Well known ways, for instance with zinc and hydrochloricacid, can be fixed more easily, but the shades in printin are less testto soap, and in particular or less festness to chlorin, than theleucocompounds of the condensation products from gellocyani-ns andaminobenzamids.

Example: 180 kg. metaminobenzamid, and kg, coelestin blue are heatedwith or Without an oxidizing agent, for example air or aromatic nitrocompounds,--during l-5 hours to 110 C. From the melt vextracted with hotWater the condensation product is obtained by filtering and washing. Thecondensution can also he performed in alcoholic solution. The product isat very crystalline body, insoluble in Water, alcohol, dilute acids and,alkelis, but soluble with a red-' violet color in concentrated sulfuricacid,

and with a red colorin concentratedhydrd The conversion into the leucocompound can be reflected as foil ws:50-.kg. of the above condensationpr duct are suspended it with stirring in 1000 liters of water and 50kg. of hydrochloric ecidl the temperature is raised to 75-80 C. and 25kg. zinc dust-in small portions are edderl at this temperature.

i I densation product of the 'As soon as the reduction which has atendency to grow stiff at once.

The reduction can also be effected with sodium hydrosulfite in presenceof alkalis, and the leuco compound be precipitated by slightlyacidulating afterward. The leuco compound is easily soluble in Water;printed with chrome mordants, 2'. e. acetate or formate of chromium, itproduces on very short steaming green blue shades of remarkable purityand of excellent fastness to light, soa and chlorin.

Iii asimilar way the condensation prodnets of gallocyanin and prune withm-aminobenzamid and of coelestin blue with paminobenzamid and thecorresponding leuco derivatives can be made.

The leuco compound from the condensation product of gallocyanin andm-aminobenzamid gives in printing clear shades of a more reddish bluethan those mentioned in the example. The leuco compound of thecondensation product of prune and m-aminobenzamid is difiicultly solubleand gives more reddish blue shades in printing than the leuco compoundof the condensation product of coelestin blue with m-aminobeir' zamid.The product obtained from coelestin blue and p-aminobenzamid is verylittle different from that obtained With the m-aminobenzamid.

What I claim and desire to secure by Letters Patent is 1. Process forthe manufacture of a con densation product of the gallocyanin series,comprising condensing a allocyanin dye with aminobenzamid other thano-aminobenzamid.

2. Process for the manufacture of a congallocy'anin series, comprisingcondensing a allocyanin dye with aminobenzamid other t iano-aminohenzamid in presence of an oxidizing agent.

Process for the manufacture of a leuco condensation product of thegallocyanin series, comprising condensing a gallocyanin dye with.aminobenzamid other than o-aminobenzamid and reducing the resultingcon-' densation product.

4. Process for the manufacture of a leuco condensation product of thegallocyanin series, comprising condensing a gallocyanin dye witha'minobenzamid other nobenzamid in presence of an oxidizing thano-amiagent and reducing theresulting condensation product.

5. Process for the manufacture of a con densation product of thegallocyanin series, comprising condensing a gallocyanin dye withm-an'iinobenzamid.

.6. Process for the manufacture of a c0ndensation product of thegallocyanin series, comprising condensing a gallocyanin dye withm-an'iinobenzaniid in presence of an oxidizing agent.

7. Process for the manufacture of a leuco condensation product of thegallocyanin series, comprising condensin a gallocyanin dye withm-aminobenzami and reducing the resulting condensation product.

8. Process for the manufacture of a leuco condensation product of thegallocyanin series, comprising condensing a gallocyanin dye withm-aminobenzamid in presence of an oxidizing agent and reducing theresulting condensation product.

9. As a new article of manufacture a condensation product of aallocyanin dye with mraminobenzamid, saicF condensation productcorresponding to the structural formula:

bONH- R representin methyl (CH) or ethyl 2 5 I 10. As a new article ofmanufacture a leuco compound of a condensation product R representingmethyl (CH or =eth l on 3) y y 5 I I v I In w tness whereof I havehereunto s1 my name in the presence of two subscri' ing witnesses Dr.EMIL WALDER W 1 tnesses i VVERNER Hammer-ma,

GEo. H. WAGN an.

